TW201024461A - Galvanized steel sheet and method for manufacturing the same - Google Patents

Galvanized steel sheet and method for manufacturing the same Download PDF

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Publication number
TW201024461A
TW201024461A TW098113978A TW98113978A TW201024461A TW 201024461 A TW201024461 A TW 201024461A TW 098113978 A TW098113978 A TW 098113978A TW 98113978 A TW98113978 A TW 98113978A TW 201024461 A TW201024461 A TW 201024461A
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Taiwan
Prior art keywords
steel sheet
zinc
aqueous solution
galvanized steel
oxide layer
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TW098113978A
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Chinese (zh)
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TWI516638B (en
Inventor
Yoichi Makimizu
Hiroshi Kajiyama
Sakae Fujita
Naoto Yoshimi
Masahiko Tada
Hiroyuki Masuoka
Katsuya Hoshino
Masayasu Nagoshi
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Jfe Steel Corp
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Priority claimed from JP2008319131A external-priority patent/JP5354165B2/en
Application filed by Jfe Steel Corp filed Critical Jfe Steel Corp
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Publication of TWI516638B publication Critical patent/TWI516638B/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer

Abstract

Provided is a method for manufacturing a galvanized steel sheet, wherein: a steel sheet is galvanized, the surface is exposed for 1 to 60 seconds to an aqueous solution with a pH of 4-6 and a temperature of 20-70 DEG C containing zinc ion with a concentration in the range of 5-100g/l, and then the steel sheet is washed and dried. An example of an ideal zinc-containing solution would be, for instance, a solution that contains zinc sulfate. The aforementioned method enables an oxide layer, mainly composed of zinc with an average thickness of no less than 10nm, to be formed on the surface of the steel sheet, thereby enabling a galvanized steel sheet with excellent press-formability to be manufactured in a stable manner and over a short period of time.

Description

201024461 六、發明說明： 【發明所屬之技術領域】 本《月係關於—種穩定製造衝壓成形時之滑動阻抗較小 且具有優異之衝麼成形性之鑛鋅鋼板的方法及具有優異之 衝壓成形性之鍍鋅鋼板。 【先前技術】 #辞鋼板以汽車車體用途為中心廣泛用於各種領域。如此 ❷用途中之鍍鋅鋼板係經由衝壓成形而供於應用。然而，錢辞 鋼板具有衝壓成形性劣於冷乾鋼板之缺點。其原因在於：衝 壓模具中鍍鋅鋼板之滑動阻抗大於冷軋鋼板。即，於模具與 調整桿中之滑動卩且抗較大之料，鍍辞鋼板難 以流入衝壓模 具内，容易引起鋼板之斷裂。 此處鑛辞鋼板中’尤其是於熔融鍍鋅處理之後經實施合 金化處理之合金化嫁融鑛鋅鋼板，因其焊接性及塗裝性優於 未經合金化處理之熔融鍍鋅鋼板，故而更適合用作汽車車體 用途。 合金化熔融鍍鋅鋼板係對鋼板實施鍍鋅之後，進行加熱處 理’使鋼板中之Fe與鍍敷層中之Zn擴散而產生合金化反 應，由此形成Fe-Zn合金相者。此巧_211合金相通常係由r 相、01相、（相所構成之皮膜，具有如下傾向：硬度及熔點 伴隨Fe濃度下降，即按Γ相―以目_^相之順序降低。因 此’由滑動性之觀點而言，高硬度、高熔點且難以引起附著 098113978 3 201024461 農度高之皮難為有效，Μ賊絲性 融鑛辞鋼㈣提高皮财之料^濃度製造㈣/ 面=幵：濃度較高之皮膜具有如下問題:於鑛敷，板界 面易於形成硬且脆之r相，知丁 η* β 現象，即所謂之粉碎。 料於發生自界面剝離之 作為解決上述問題之方法，於專利文獻^及專利文獻2 中揭不有-種技術，該技術係對錢鋅鋼板之表面實施電解處 理、浸潰處理、塗佈氧化處理或加熱處理，藉此形成以Zn〇 為主體之氧化膜，從而提高焊接性、加工性。 然而’於將專利文獻1及2之技術適用於合金倾融鑛辞 鋼板之情形時，由於合金化熔融鍍敷鋼板中存在A〗氧化 物，故導致表面反應性劣化，而且表面之凹凸較大，故而無 法穩定獲得衝壓成形性之改善效果。即，因表面之反應性較 低，故而即便進行電解處理、浸潰處理、塗佈氧化處理及加 熱處理等，亦難以於表面形成既定之皮膜，導致膜厚於反應 性較低之部分，即A1氧化物量較多之部分處減薄。又，因 表面之凹凸較大，故而於衝壓成型時直接與衝壓模具接觸者 為表面之凸部，而凸部中膜厚較薄之部分與模具之接觸部中 之滑動阻抗變大，故無法充分獲得衝壓成形性之改善效果。 因此，於專利文獻3中揭示有一種技術，該技術係對鋼板 進行熔融鍍鋅之後，藉由加熱處理進行合金化，進而實施調 質軋壓之後，與具有pH缓衝作用之酸性溶液進行接觸，保 098113978 4 201024461 持1〜30秒後，進行水洗，藉此於鍍敷表層形成氧化物層。 作為同樣於未實施合金化處理之熔融鍍鋅鋼板之表面平 坦部上均勻地形成氧化物層的方法，於專利文獻4中揭示有 一種方法，該方法係使調質軋壓後之熔融鑛鋅鋼板與具有 pH緩衝作用之酸性溶液接觸，然後，於鋼板表面形成有酸 性〉谷液之液膜之狀態下保持既定時間之後，進行水洗、乾燥 者。 • 專利文獻1 :日本專利特開昭53-60332號公報 專利文獻2:日本專利特開平2-190483號公報 專利文獻3:日本專利特開2003-306781號公報 專利文獻4:曰本專利特開2004-3004號公報 於適用上述專利文獻3及4中揭示之技術之情形時，於先 則之製造條件下，可獲得良好之衝壓成形性。然而，近年來， 由於生產性之提高’而期望開發一種以更短時間生成更厚之 參氧化膜之製造方法，於上述條件下進行時，藉由專利文獻3 及4中揭示之技術’有時無法形成充分之氧化膜，從而無法 獲得良好之衝壓成形性。 本發明之目的在於鑒於上述情況，而提供一種短時間亦可 穩定製造具有優異之衝壓成形性之鍍鋅鋼板的製造方法及 具有優異之衝壓成形性之鍍鋅鋼板。 【發明内容】 本發明者等人為了解決上述課題，而不斷進行積極研究。 098113978 5 201024461 其結果，獲得以下見解。 專利文獻3及4之技術中使用之酸性溶液，因促進辞之溶 解之目的，而具有pH緩衝作用。因此，認為使得阳之上 升延緩，導致氧化物層之形成緩慢。而且，為了以自錄敷皮 膜溶出之鋅補充形成氧化物層之鋅，故而氧化.生^時間 包括鋅之溶出時^其結果，認為難以短時間内生成較厚^ 氧化膜。 、因此’本發明者等人研究出—種技術，該技術係藉由使生 成氧化膜之水溶液中預先含有鋅離子，從而省略鋅之溶出時 間’可依更短時間生成氧化膜者。㈣，僅藉由使水溶液中 =:、ίΓ子，則無法促進氧化膜之形成。尤其是，即便 4t以專利文獻3及4之實施例中所示 鋅’亦無法促魏储之形成。 3有 ^認為其原因在於：於專利文獻3及4之技術中， 冷出之间時所弓丨起之氫離子之 、 升而成為易於U栳备“ *仔表面附近之PH上 易於生成鋅氧化物之環境， ，中含有鋅離子，财會弓丨起表面 水 無法形成易於生成鋅氧化物之環境。 升’從而 此本發明者等人研究出一種技 之阳為易於生成鋅氧化物之溶液 情形:可藉由使處理液之阳為4〜6，者。而且，發現如下 鋅略微溶& 、 而利用使鍍敷皮臈之 出所引起之表面PH之微小上升，使辞以氣氧化物201024461 VI. Description of the Invention: [Technical Fields of the Invention] This "monthly method" is a method for stably producing a zinc-zinc steel sheet having a small sliding resistance and excellent punchability during press forming, and has excellent press forming. Galvanized steel. [Prior Art] #辞板 is widely used in various fields centering on the use of automobile bodies. The galvanized steel sheet used in such an application is applied by press forming. However, the Qianzi steel plate has the disadvantage that the press formability is inferior to that of the cold dry steel sheet. The reason is that the sliding resistance of the galvanized steel sheet in the pressing die is larger than that of the cold rolled steel sheet. That is, the sliding of the mold and the adjusting rod and the resistance to the larger material make it difficult for the plated steel sheet to flow into the stamping mold, which easily causes the steel sheet to break. Here, the alloyed martensite zinc steel plate which is alloyed after the hot-dip galvanizing treatment is superior to the non-alloyed hot-dip galvanized steel sheet because of its weldability and coating property. Therefore, it is more suitable for use as a car body. In the alloyed hot-dip galvanized steel sheet, after the steel sheet is galvanized, heat treatment is performed, and the Fe in the steel sheet and the Zn in the plating layer are diffused to form an alloying reaction, thereby forming an Fe-Zn alloy phase. This alloy _211 alloy phase is usually composed of r phase, 01 phase, and (phase) film, and has the following tendency: hardness and melting point decrease with the concentration of Fe, that is, in the order of Γ phase - in the order of the phase. From the point of view of slidability, high hardness, high melting point and difficulty in causing adhesion 098113978 3 201024461 The high degree of soil is difficult to be effective, and the thief silky minerals refining steel (4) to improve the material of the skin ^ concentration manufacturing (four) / surface = 幵: The film with higher concentration has the following problems: in the mineral deposit, the interface of the plate is easy to form a hard and brittle r phase, and the phenomenon of η η* β, so-called pulverization, is the method for solving the above problem. There is no such technique in Patent Document 2 and Patent Document 2, which performs electrolytic treatment, impregnation treatment, coating oxidation treatment or heat treatment on the surface of a zinc-zinc steel sheet, thereby forming Zn 〇 as a main body. The oxide film improves the weldability and the workability. However, when the techniques of Patent Documents 1 and 2 are applied to the case where the alloy is poured into the ore plate, since the A-form oxide exists in the alloyed melt-plated steel sheet, Lead to the table Since the surface reactivity is deteriorated and the unevenness of the surface is large, the effect of improving the press formability cannot be stably obtained. That is, since the reactivity of the surface is low, even the electrolytic treatment, the impregnation treatment, the coating oxidation treatment, and the heat treatment are performed. Etc., it is also difficult to form a predetermined film on the surface, resulting in a film thickness in a portion where the reactivity is low, that is, a portion where the amount of A1 oxide is large, and further, since the surface has a large unevenness, it is directly formed during press forming. The contact person of the stamping die is a convex portion of the surface, and the sliding resistance in the contact portion between the portion where the film thickness is thin and the mold portion in the convex portion becomes large, so that the effect of improving the press formability cannot be sufficiently obtained. Therefore, in Patent Document 3 A technique is disclosed in which the steel sheet is subjected to hot-dip galvanizing, alloyed by heat treatment, and then subjected to tempering and rolling, and then contacted with an acidic solution having a pH buffering effect, and 098113978 4 201024461 holds 1 After ~30 seconds, it is washed with water to form an oxide layer on the plating surface layer. As a molten galvanized steel sheet which is not subjected to alloying treatment. A method of uniformly forming an oxide layer on a flat surface portion, and Patent Document 4 discloses a method of contacting a molten ore zinc steel sheet after quenching and tempering with an acidic solution having a pH buffering effect, and then, In the state in which the liquid film is formed on the surface of the steel sheet, the liquid film is formed in a state of a liquid film, and then it is washed with water and dried. Patent Document 1: Japanese Patent Laid-Open No. Sho 53-60332 Patent Document 2: Japanese Patent Laid-Open No. 2- In the case of applying the technique disclosed in the above Patent Documents 3 and 4, the case of the prior art is disclosed in Japanese Laid-Open Patent Publication No. 2003-306781. Under the manufacturing conditions, good press formability can be obtained. However, in recent years, it has been desired to develop a manufacturing method for producing a thicker oxidized film in a shorter period of time due to an increase in productivity. Under the above conditions, the techniques disclosed in Patent Documents 3 and 4 have When a sufficient oxide film cannot be formed, good press formability cannot be obtained. In view of the above, an object of the present invention is to provide a method for producing a galvanized steel sheet having excellent press formability and a galvanized steel sheet having excellent press formability in a short period of time. SUMMARY OF THE INVENTION The inventors of the present invention have continuously conducted active research in order to solve the above problems. 098113978 5 201024461 As a result, the following insights were obtained. The acidic solution used in the techniques of Patent Documents 3 and 4 has a pH buffering effect for the purpose of promoting dissolution of the word. Therefore, it is considered that the rise above the yang is delayed, resulting in a slow formation of the oxide layer. Further, in order to replenish the zinc which forms the oxide layer by the zinc eluted from the self-recorded coating film, the oxidation time is included when the zinc is eluted, and it is considered that it is difficult to form a thick oxide film in a short time. Therefore, the inventors of the present invention have developed a technique in which an oxide film is formed in a shorter period of time by arbitrarily containing zinc ions in an aqueous solution in which an oxide film is formed, thereby omitting the elution time of zinc. (4) The formation of an oxide film cannot be promoted only by making =:, Γ 水溶液 in an aqueous solution. In particular, even if 4t is shown in the examples of Patent Documents 3 and 4, zinc is not promoted. (3) It is believed that the reason is that, in the techniques of Patent Documents 3 and 4, the hydrogen ions which are bowed between the cold and the rise rise to become easy to prepare for the U-preparation. In the environment of oxides, zinc ions are contained in the environment, and the surface of the money can not form an environment in which zinc oxide is easily formed. Thus, the inventors of the present invention have developed a technique for the easy formation of zinc oxide. In the case of a solution, it is possible to make the cation of the treatment liquid 4 to 6. Further, it is found that the zinc is slightly dissolved & and the surface pH caused by the plating of the coating is slightly increased, so that the gas is oxidized. Object

°98113978 J 201024461 之形式生成。 本發明係基於上述見解開發而成者，其主旨如下所述。 [1] 一種鍍鋅鋼板之製造方法，其係對鋼板實施鍍鋅之 '後，使鋼板與水溶液進行接觸處理，並於接觸處理結束之後 保持1〜60秒，然後進行水洗.乾燥’藉此於鋼板表面形成 氧化物層者，其特徵在於：對鋼板進行接觸處理之上述水溶 液，係以辞離子濃度為5〜100 g/Ι之範圍含有辞離子，且 ❹ pH為4〜6 ’液體溫度為20〜70°C。 [2] 如上述[1]之鍍鋅鋼板之製造方法，其中，上述水溶液 中含有鋅之硫酸鹽。 [3] 如上述[1]或[2]之鍍鋅鋼板之製造方法，其中，與上述 水溶液接觸之後形成於鋼板表面之液膜為5〜3〇 g/m2。 [4] 一種鍍辞鋼板，其特徵在於：其係藉由上述[丨]至[3]中 任-項之鍍鋅鋼板之製造方法而製造者，且於鋼板表面形成 平均厚度1G nm以上之主要含有鋅作為金屬成分之氧化物 層0 再者’於本發明中’所謂锻鋅鋼板，係指使以辞為主成分 之皮膜形成於表面之魏鋼板，包括__鋼板（簡稱為 GI鋼板）、合金化熔融錢鋅鋼板(簡稱為ga鋼板）、電錢辞 鋼板(簡稱為EG鋼板)、蒸鍍鋅鋼板或含有Fe、A1、Ni、 MgCo等合金元素之合金鍍鋅鋼板等。 【實施方式】 098113978 7 201024461 本發明係一種鍍鋅鋼板 鑛鋅之後，使練於切造方法，其補由對鋼板實施 結束之後保持N60秒，2進行接觸處理，並於接觸處理 鋼板表面形成氧化物層時進行水洗.乾燥’從而於鑛鋅 為5〜l(X)g/W_含 爾于澴度 為如〜啊。如此，本發阳為4〜6,液體溫度 成含有既定濃度之_子且^重要之必要條件及特徵係製 作為對鋼板進行接觸處理之水:體溫度的水溶液’ mm lAr ^ 尺，合液。藉此，由於確保良好之 衝壓成祕故而可依短相形成充分之氧化物層。 再者，所謂接觸處理社杏 步驟結束讀，於対浸潰纽之㈣係指浸潰 霧處理之_係指倾㈣結束之後， 而於輥塗之情形軸_步驟結束之後。 作為對鋼板進行接觸處理之水溶液，可藉由使用含有辞離 子之水溶液，而雀略鋅之溶出時間。此時，使鋅離子為5〜 100g/l之範圍來料_子濃度。若_子濃絲達5g/l， 則無法供給充分之鋅，從而無法形成氧化物層m 右超過100、g/_l，則所形成之氧化物層中所含之硫酸濃度會 變高’此後進行之化成處理步驟中氧化物溶解時，有污染處 理液之虞。 為了形成穩定之鋅化合物作為氧化物層，較佳為以硫酸鹽 之形式添加鋅離子。於以硫酸鹽之形式添加鋅離子之情形 時’可認為硫酸離子被吸取至_成之氧化物層中，具有使 098113978 201024461 氧化物層穩定之效果。 又，如上所述，僅藉由使處理液中預先含有鋅離子，則無 法促進氧化膜之形成。因此，於本發明中，必須使pH達到 易於生成鋅氧化物之pH4〜6。若使處理液之pH達到4〜6, 則由於鍍敷皮膜之鋅略微溶出而引起之表面pH之微小上 升，而鋅以氫氧化物生成。 作為該等之結果，便可省略鋅之溶出時間，且，可生成鋅 •氧化物。於pH超過6之情形時，水溶液中辞離子將會沉殿 (形成氫氧化物）’而無法以氧化物形成於鋼板表面。又，於 pH未達4之情形時，如上所述，pH上升延遲將阻礙氧化物 層之形成。 使水溶液之溫度為2G〜7G°C。因氧化物層之形成反應係 於與水溶液接觸後，保持規定時間時產生，故而有效的是將 保持時之鋼板溫度控制為20〜7(rc之範圍。若未達2〇。〇， 鲁則氧化物層之生成反應需要長時間，導致生產性下降。另一 方面’於㈣7G°C之情科，反應將相對地快速進行，而 相反地於鋼板表面易於產生處理不均。 專利文獻3及4中使用之水溶液之特徵為呈酸性，且具有 PH緩衝作用。然而，因本發明中使用含有辞離子之水溶液， 故而即便提高水溶液之pH而使鋅不充分溶解，亦可形成充 分之氧化物層。又，可認為pH上升快速有利於形成氧化物。 故而，未必需要pH緩衝作用。 098113978 9 201024461 於本發針’若_板表面接觸之水溶液中含有辞，則可 穩疋形成π動性優異之氧化物層，故而即便水溶液中有意地 含有其他金·子或無機化合物等作為㈣，林會損及本 發明之效果。而且，印便N、P、B、a、Na、Mn、Ca、Mg Ba、Sr、Si等進人氧化物層+，只要不損及本發明之效果 便可適用該等。 較理想的是，於賴鋅鋼板與包含以上元素之水溶液接觸 之後’該水溶液以較薄之液膜狀存在於鋼板表面。其原因在 於：若存在於鋼板表面之水溶液之量好，則即便鋅產生溶 解，水溶液之PH亦難以上升，形成氧化物層為止需要長時 間。根據峨點’較佳且有效的是將賴於鋼板表面之水容 液膜之量調整為3°咖2以下。又，為防止液膜乾燥，較佳 為5 g/m2以上之液膜量。根據上述觀點，較佳為，使與上 返水溶液接狀後形成於鋼板表®之顏為5〜3Gg/m2e再 者，水溶液膜量之調整可藉由擠雖、去除氣體等進行。 又，於水紐巾進行浸潰之後直至水洗為止之時間（水洗 為止之保持時間)設為1〜6〇移、。若水洗為止之時間未達i 心則形成有充分之氧化物層之前，水溶液會被沖走，故而 無法獲得滑動性之提高效果。另—方面，若保㈣間超過 60秒，則會導致生產性下降。因本發明之目的在於可以短 時間進行穩定製造，故而根據充分發揮本發明之效果之觀 點’而將保持時間設為60秒以下。 098113978 10 201024461 根據上述觀點，於本發明之鑛敷鋼板之表面，可獲得主 含有鋅作為金屬成分且平均厚度為1Gnm以上之氧化物層。 :者’以辞為主體係指含有5〇質量%以上之鋅作為‘ 成刀。 再者’所謂本發明之氧化物層，健包含主要含有辞作為 金屬成分之氧化物及/或氫氧化物等之層。該氧化物層之平 均厚度必須為10nm以上。若氧化物層之平均厚度薄到未達 ❿H)mn’騎赌動阻抗之效果將不充分ϋ面若含 有鋅作為必須成分之氧化物層之平均厚度超過刚⑽則 存在衝壓加工中皮膜遭破壞而使滑動阻抗上升，又，焊接性 下降之傾向’故而欠佳。 再者，使鍍鋅鋼板於含有鋅之水溶液_騎接觸處理之方 法’並不特別限制’存在有將鐘敷鋼板浸潰於水溶液之方 去對鑛敷鋼板喷霧水溶液之方法，經由塗佈親將水溶液塗 佈於㈣鋼板之方法等，較理想的是最終以較薄之液膜狀存 在於鋼板表面。 又’關於製造本發明之合金恤融鱗鋼板，必須於錢敷 槽中添加Α1 ’但並不制限絲A1料之添加元素成分。 即’除了 A1以外’即便含有或者添加凡、讥、以、％、Forming in the form of °98113978 J 201024461. The present invention has been developed based on the above findings, and the gist thereof is as follows. [1] A method for producing a galvanized steel sheet, which is characterized in that after the steel sheet is galvanized, the steel sheet is brought into contact with the aqueous solution, and is kept for 1 to 60 seconds after the end of the contact treatment, and then washed with water. The oxide layer formed on the surface of the steel sheet is characterized in that the aqueous solution subjected to the contact treatment on the steel sheet contains a reciprocating ion in a range of 5 to 100 g/Ι, and the pH of the liquid is 4 to 6 'liquid temperature. It is 20~70 °C. [2] The method for producing a galvanized steel sheet according to the above [1], wherein the aqueous solution contains zinc sulfate. [3] The method for producing a galvanized steel sheet according to the above [1] or [2] wherein the liquid film formed on the surface of the steel sheet after contact with the aqueous solution is 5 to 3 〇 g/m 2 . [4] A plate-plated steel sheet which is produced by the method for producing a galvanized steel sheet according to any one of the above [丨] to [3], and which has an average thickness of 1 G nm or more on the surface of the steel sheet. An oxide layer mainly containing zinc as a metal component. Further, in the present invention, a so-called wrought-zinc steel plate refers to a Wei steel plate in which a film containing a main component is formed on a surface, including a __ steel plate (referred to as a GI steel plate). Alloyed molten zinc-zinc steel plate (abbreviated as ga steel plate), electric money plate (abbreviated as EG steel plate), vapor-dip galvanized steel plate or alloy galvanized steel sheet containing alloying elements such as Fe, A1, Ni, MgCo, and the like. [Embodiment] 098113978 7 201024461 The present invention is a galvanized steel sheet of zinc, which is subjected to a cutting method, which is maintained for N60 seconds after the completion of the steel sheet, 2 is subjected to contact treatment, and oxidation is formed on the surface of the contact treated steel sheet. When the layer is washed, it is washed. The resulting zinc is 5~l(X)g/W_ of the mineral zinc. In this way, the present temperature is 4 to 6, and the liquid temperature is a predetermined concentration and the necessary conditions and characteristics are made as a water solution for contacting the steel sheet: body temperature of the aqueous solution 'mm lAr ^ ft, the liquid . Thereby, a sufficient oxide layer can be formed in a short phase by ensuring good stamping. Further, the so-called contact treatment of the apricot step is completed, and the immersion of the 対 纽 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( As the aqueous solution for the contact treatment of the steel sheet, the dissolution time of the zinc can be obtained by using an aqueous solution containing a rhodium. At this time, the zinc ion is made to have a concentration of 5 to 100 g/l. If the _ sub-concentration reaches 5 g/l, sufficient zinc cannot be supplied, so that the oxide layer m cannot be formed to the right and exceeds 100, g/_l, and the concentration of sulfuric acid contained in the formed oxide layer becomes high. In the case where the oxide is dissolved in the chemical conversion treatment step, there is a contamination of the treatment liquid. In order to form a stable zinc compound as an oxide layer, it is preferred to add zinc ions in the form of a sulfate. In the case where zinc ions are added in the form of a sulfate, it is considered that the sulfate ions are absorbed into the oxide layer, and the effect of stabilizing the oxide layer of 098113978 201024461 is obtained. Further, as described above, the formation of the oxide film cannot be promoted only by preliminarily containing zinc ions in the treatment liquid. Therefore, in the present invention, it is necessary to bring the pH to pH 4 to 6 which is liable to form zinc oxide. When the pH of the treatment liquid is 4 to 6, the surface pH is slightly increased due to the slight elution of the zinc in the plating film, and zinc is formed as a hydroxide. As a result of these, the dissolution time of zinc can be omitted, and zinc oxide can be formed. When the pH exceeds 6, the re-ioning ions in the aqueous solution will sink (formation of hydroxide) and cannot form oxides on the surface of the steel sheet. Further, when the pH is less than 4, as described above, the delay in pH rise will hinder the formation of the oxide layer. The temperature of the aqueous solution was made 2G to 7G °C. Since the formation reaction of the oxide layer occurs after contact with the aqueous solution for a predetermined period of time, it is effective to control the temperature of the steel sheet at the time of holding to 20 to 7 (the range of rc. If it is less than 2 〇. 〇, Lu Ze The formation reaction of the oxide layer takes a long time, resulting in a decrease in productivity. On the other hand, in the case of (4) 7G ° C, the reaction will proceed relatively quickly, and conversely, the surface of the steel sheet is liable to cause uneven processing. Patent Document 3 and The aqueous solution used in 4 is characterized by being acidic and having a pH buffering effect. However, since an aqueous solution containing a reciprocating ion is used in the present invention, sufficient oxide can be formed even if zinc is not sufficiently dissolved by increasing the pH of the aqueous solution. In addition, it can be considered that the pH rise is fast to facilitate the formation of oxides. Therefore, pH buffering is not necessarily required. 098113978 9 201024461 In the aqueous solution of the hairpin's surface contact, it can be stabilized to form π-movability. Since the oxide layer is excellent, even if an aqueous solution intentionally contains other gold or inorganic compounds or the like as (4), the forest may impair the effects of the present invention. Then, N, P, B, a, Na, Mn, Ca, Mg Ba, Sr, Si, etc. may be applied to the oxide layer + as long as the effect of the present invention is not impaired. After the zinc steel sheet is contacted with the aqueous solution containing the above elements, the aqueous solution is present on the surface of the steel sheet in a thin liquid film. The reason is that if the amount of the aqueous solution present on the surface of the steel sheet is good, even if the zinc is dissolved, the pH of the aqueous solution is also It is difficult to rise, and it takes a long time to form an oxide layer. According to the defect, it is preferable and effective to adjust the amount of the water-retaining film on the surface of the steel sheet to 3° or less. In addition, in order to prevent the liquid film from drying, Preferably, the amount of the liquid film is 5 g/m 2 or more. According to the above viewpoint, it is preferable to adjust the amount of the aqueous solution by forming the surface of the steel sheet surface after the contact with the upper aqueous solution is 5 to 3 Gg/m 2 e. It can be carried out by squeezing, removing gas, etc. The time until the water washing is performed after the water towel is dipped (the holding time until washing) is 1 to 6 、, and the time until washing is not reached. The heart will form a sufficient layer of oxide before the aqueous solution will If it is washed away, the effect of improving the slidability cannot be obtained. On the other hand, if it is more than 60 seconds between the guarantees (4), the productivity is lowered. The object of the present invention is to enable stable production in a short period of time, so that the present invention can be fully utilized. According to the above viewpoint, on the surface of the mineral-coated steel sheet of the present invention, an oxide mainly containing zinc as a metal component and having an average thickness of 1 Gnm or more can be obtained. Layer: The term "mainly refers to a system containing more than 5% by mass of zinc as a "knife. Further" the so-called oxide layer of the present invention contains an oxide and/or hydrogen mainly containing a metal component. A layer of an oxide or the like. The average thickness of the oxide layer must be 10 nm or more. If the average thickness of the oxide layer is as thin as less than H), the effect of riding the gambling resistance will be insufficient. If the average thickness of the oxide layer containing zinc as an essential component exceeds the thickness (10), the film may be damaged during the stamping process. On the other hand, the sliding resistance is increased, and the tendency of the weldability is lowered, which is not preferable. In addition, the method of galvanizing the galvanized steel sheet in the aqueous solution containing zinc is not particularly limited to the method of spraying the aqueous solution to the mineralized steel sheet by impregnating the steel sheet with the aqueous solution. The method of applying an aqueous solution to the (four) steel sheet, etc., is preferably carried out on the surface of the steel sheet in the form of a thin liquid film. Further, in order to manufacture the alloy-tied scale-scaling steel sheet of the present invention, it is necessary to add Α1' to the money preparation tank, but it is not limited to the additive element component of the silk A1 material. That is, 'other than A1', even if it contains or adds 凡, 讥, 、, %,

Mg Μη Ni Ti、Li、Cu等’只要不損及本發明之效果， 亦可應用。 [實施例] 098113978 11 201024461 其次’藉由實施例更詳細說明本發明。 於板厚為0.8 mm之冷軋鋼板上，實施每一單面之附著量 為45 g/m2、A1濃度為〇 2〇質量％之熔融鍍鋅之後，進行調 質軋壓，從而製作GI鋼板。又，於板厚為0 8 mm之冷軋 鋼板上，藉由常法之合金化熔融鍍鋅法，形成每一單面之鍍 敷附著量為45 g/m2、Fe濃度為10質量％、A1濃度為〇 2〇 貝里％之鍍敷皮膜，進而進行調質軋壓，製作GA鋼板。又， 於板厚為0.8 mm之冷軋鋼板上，藉由常法之鍍敷鋅法，製❿ 作具有每一單面之鍍敷附著量為30 g/m2之鍍敷皮膜的Eg 鋼板。 、接者’使用圖1所示之構成之處理設備，形成氧化物層。 首先’將藉由上述處理獲得之以鋼板、GA鋼板及eg鋼板 等鋼板S ’於溶液槽2中’浸潰於表1-1及表1-2所示之處 理液成分、溫度及阳不同之水溶液中。繼而，藉由擠㈣ 3來》周整鋼板表面之液膜量。液膜量之調整係藉由改變擠壓 〇 f之壓力而進行。繼而，使該等鋼板S直接穿過清洗槽5、 清洗槽6,於清洗槽7中將就之溫水嘴霧於鋼板上進行清 洗，並於乾燥機8中進行乾燥，從而於錄表面形成氧化物 層。再者，可於溶液槽2之前方設置清洗槽工。 ;，液槽2中進行浸潰處理之水溶液，以添加辞離子之目 的’而使用添加有規定量之硫酸鋅七水合物之水溶液。再 者，部分為了進行比較，亦使用利用硫酸對含有2〇 g几 098113978 12 201024461 之乙酸鈉之溶液進行pH調整後之溶液。 水洗為止之保持時間係藉由擠壓輥3來調整液膜量，直至 於清洗槽7中開始清洗為止之時間，亦製成可藉由改變線速 度來進行調整，並且，一部分使用擠壓輥3擠出側之淋式水 洗裝置4於擠壓後立即清洗鋼板者。 其次，對如上所述製作之鋼板，判定作為汽車用外殼是否 具有充分之外觀，並且作為簡單評價衝壓成形性之方法，實 〇 施摩擦係數之測定，以及以更詳細模擬實際成形性之目的實 施球頭伸展試驗。再者，測定方法為如下所述。 (1)衝壓成形性評價試驗(摩擦係數測定試驗） 為了對衝壓成形性進行評價，而以如下方式測定各供試材 料之摩擦係數。 圖2係表示摩擦係數測定裝置之概略前視圖。如圖2所 示，將取自供試材料之摩擦係數測定用樣本11固定於樣本 • 台12，樣本台12固定於可水平移動之滑台13之上表面。 於滑台13之下表面，設置有具有與此處連接之滾筒14的可 上下移動之滑台支撐台15,藉由向上推動該滑台支撐台 15,而將用以測定調整桿16對摩擦係數測定用樣本11之擠 壓荷重N的第1荷重元17安裝於滑台支撐台15。為了測定 於使上述擠壓力進行作用之狀態下使滑台13沿著軌道19 水平移動之滑動阻抗力F，而將第2荷重元18安裝於滑台 13之一方端部。再者，作為潤滑油，將衫村化學公司製造 098113978 13 201024461 ===-_塗佈於摩擦係數測_本 圖3上及_ 4係表示所使狀調整桿之形狀.尺寸 體圖。调整桿16之下表面崎壓 行滑動所示之調整桿16之形料寬^;之狀態進 之嚕叙。狀為寬度l〇mm，樣本 向長度為12麵，滑動方向兩端之下部由曲率為 4.5mmR之曲面禮出她蔽接士 丨由曲羊為 曲面構成，㈣樣本之難桿之下表面具有寬度 ^職且滑動方向長度為3mm之平面。圖4所示之調整 :之形狀為寬度10mm’樣本之滑動方向長度為69麵， =方向兩端之下部由㈣為45 mmR之曲面構成擠壓 樣本之_桿之下表面具有寬度為1G _且滑動方向長度 為60 mm之平面。 以如下所示之兩個條件’進行摩擦係數測定試驗。Mg Μη Ni Ti, Li, Cu, etc. can be applied as long as the effects of the present invention are not impaired. [Examples] 098113978 11 201024461 Next, the present invention will be described in more detail by way of examples. On a cold-rolled steel sheet having a thickness of 0.8 mm, a galvanized steel sheet was prepared by subjecting each single-sided adhesion amount to 45 g/m2 and A1 concentration to 〇2〇 mass% of hot-dip galvanizing. . Further, on the cold-rolled steel sheet having a thickness of 0 8 mm, the plating adhesion amount per one side is 45 g/m 2 and the Fe concentration is 10% by mass by a conventional alloying hot-dip galvanizing method. The A1 concentration is a plating film of 〇2 〇Berry%, and further temper rolling is performed to produce a GA steel sheet. Further, on a cold-rolled steel sheet having a thickness of 0.8 mm, an Eg steel sheet having a plating film having a plating amount of 30 g/m 2 per one side was produced by a conventional zinc plating method. The receiver uses the processing equipment of the configuration shown in Fig. 1 to form an oxide layer. First, 'the steel sheet S' obtained by the above-mentioned treatment, the steel sheet S' such as a steel sheet, a GA steel sheet, and an eg steel sheet are immersed in the solution tank 2, and the composition, temperature, and temperature of the treatment liquid shown in Table 1-1 and Table 1-2 are different. In the aqueous solution. Then, by squeezing (4) 3, the amount of liquid film on the surface of the steel plate is measured. The adjustment of the liquid film amount is carried out by changing the pressure of the extrusion 〇 f . Then, the steel sheets S are directly passed through the cleaning tank 5 and the cleaning tank 6, and the warm water nozzle is sprayed on the steel sheet in the cleaning tank 7, and is dried in the dryer 8, thereby forming on the recording surface. Oxide layer. Furthermore, a cleaning tank can be provided in front of the solution tank 2. The aqueous solution subjected to the impregnation treatment in the liquid bath 2 is an aqueous solution to which a predetermined amount of zinc sulfate heptahydrate is added for the purpose of adding the excimer. Further, for comparison, a solution obtained by pH-adjusting a solution containing 2 g of a few 098113978 12 201024461 sodium acetate using sulfuric acid was also used. The holding time until the washing is performed by the pressing roller 3 to adjust the amount of the liquid film until the cleaning is started in the washing tank 7, and the adjustment can be made by changing the linear velocity, and a part of the pressing roller is used. 3 The one-side washing device 4 on the extrusion side cleans the steel plate immediately after extrusion. Then, it is determined whether or not the steel sheet produced as described above has a sufficient appearance, and as a method for simply evaluating the press formability, the measurement of the coefficient of friction and the purpose of simulating the actual formability in more detail are carried out. Ball head extension test. Furthermore, the measurement method is as follows. (1) Press Formability Evaluation Test (Coefficient of Friction Measurement) In order to evaluate the press formability, the friction coefficient of each test material was measured as follows. Fig. 2 is a schematic front view showing a friction coefficient measuring device. As shown in Fig. 2, the sample 11 for measuring the coefficient of friction taken from the test material is fixed to the sample stage 12, and the sample stage 12 is fixed to the upper surface of the slide table 13 which is horizontally movable. On the lower surface of the slide table 13, there is provided a slide support table 15 having a roller 14 connected thereto, which is movable up and down, and is used to measure the friction of the adjustment rod 16 by pushing the slide support table 15 upward. The first load cell 17 of the squeeze load N of the coefficient measurement sample 11 is attached to the slide table 15 . In order to measure the sliding resistance force F for horizontally moving the slide table 13 along the rail 19 in a state in which the above-described pressing force is applied, the second load cell 18 is attached to one end portion of the slide table 13. In addition, as a lubricating oil, it is manufactured by Shoucun Chemical Co., Ltd. 098113978 13 201024461 ===-_ is applied to the coefficient of friction measurement. Fig. 3 and _ 4 show the shape and size of the shape adjustment rod. The bottom surface of the adjustment rod 16 is slid. The shape of the adjustment rod 16 shown by the slide is shown in the state of the width. The width is l〇mm, the length of the sample is 12, and the lower part of the sliding direction is made of a curved surface with a curvature of 4.5mmR. The mask is made of curved sheep. (4) The lower surface of the sample has a concave surface. A plane with a width of 3 mm and a sliding direction of 3 mm. The adjustment shown in Fig. 4 is characterized by a width of 10 mm. The length of the sliding direction of the sample is 69, and the lower surface of the = direction is composed of a curved surface of (45) 45 mmR. The lower surface of the rod has a width of 1 G _ The plane with a sliding direction length of 60 mm. The friction coefficient measurement test was carried out under the two conditions ' as shown below.

[條件1J 使用圓3所示之調整桿，並設定為擠壓荷重N : 400 kgf，[Condition 1J Use the adjustment rod shown by circle 3 and set the extrusion load N: 400 kgf,

樣本之㈡丨速度㈣13之水平移動速度）：lGGem/min。 [條件2JThe sample (b) 丨 speed (four) 13 horizontal moving speed): lGGem / min. [Condition 2J

使用圓4所示之調整桿，並設定為擠壓荷重N : 400 kgf， 樣本之牵引速度(滑台13之水平移動速度）：20cm/min。 供試材料與調整桿間之摩擦係數以利用式：V = F/N 算 出。 (2)球頭伸展試驗 098113978 201024461 對2〇〇X200酬尺寸之供試材料，使用⑼—之衝壓 機，藉由液_脹試驗機進行伸展成形，朗定產生斷裂時 之最大成形高度。此時’以阻止材料流人為目的，而施加 100 Ton之壓邊力’並將潤滑油僅塗佈於衝壓機所接觸之 面。所使用之潤滑油係與上述摩擦係數測定試驗相同者。 (3)氧化物層之厚度（氧化膜厚）之測定 將形成有膜厚為96 nm之熱氧化Si〇2膜之si晶圓用作參 # 照物質，藉由螢光X射線分析裝置測定〇·ΚαΧ射線，藉 此算出經Si〇2換算之氧化層之平均厚度。分析面積為30 mm^ ° 根據上述處理所獲得之試驗結果示於表M及表1-2。Use the adjustment rod shown by circle 4 and set the extrusion load N: 400 kgf, the traction speed of the sample (the horizontal movement speed of the slide table 13): 20 cm/min. The coefficient of friction between the test material and the adjustment rod is calculated by the formula: V = F/N. (2) Ball-end stretching test 098113978 201024461 For the test material of 2〇〇X200 resize, use the press of (9)-, and perform the stretching forming by the liquid-expansion tester to determine the maximum forming height at break. At this time, a blanking force of 100 Ton was applied to prevent the material from flowing, and the lubricating oil was applied only to the surface of the press. The lubricating oil used was the same as the above-described friction coefficient measurement test. (3) Measurement of Thickness of Oxide Layer (Oxide Film Thickness) A Si wafer on which a thermally oxidized Si〇2 film having a film thickness of 96 nm was formed was used as a reference material, and was measured by a fluorescent X-ray analyzer. The average thickness of the oxide layer in terms of Si〇2 was calculated by 〇·ΚαΧ ray. The analysis area was 30 mm ^ ° The test results obtained according to the above treatment are shown in Table M and Table 1-2.

098113978 15 201024461 [表 1-1]098113978 15 201024461 [Table 1-1]

No. 供試 材料 使用溶液 pH 溶液 溫度 賴量 (g/mz) 水洗為止 之時間 (秒） 氧化 膜厚 (nm) 摩齡數 最大成 形高度 (ran) 鋼板 外觀 備註 pH 緩衝劑 Zn 紐1 餅2 1 GA — — — — — 一 8 0.180 0.223 35.0 〇 比較例1 2 乙酸納 (20 g/L) — 2.0添 加硫酸 35〇C 10 10 15 0.149 0.190 36.5 〇 fcbfe例 2 3 10 30 30 0.128 0.165 38.1 〇 比較例3 4 10 60 42 0.120 0.163 39.3 〇 比較例4 5 — 5.0添 加硫酸 35〇C 10 10 8 0.183 0.219 35.6 〇 比較例5 6 10 30 8 0.179 0.221 35.9 〇 比較例6 7 10 60 8 0.180 0.217 35.9 〇 比較例7 8 — 2.5 g/1 5.6 35〇C 10 10 12 0.148 0.200 36.5 〇 比較例8 9 10 30 25 0.140 0.174 37.9 〇 比較例9 10 10 60 32 0.132 0.163 38.9 〇 比較例10 11 5 g/1 5.5 35〇C 10 10 18 0.138 0.187 37.6 〇 本發明例1 12 10 30 32 0.123 0.166 39.1 〇 本發明例2 13 10 60 43 0.122 0.163 39.5 〇 本發明例3 14 10 g/1 5.2 35〇C 10 10 25 0.134 0.174 39.0 〇 本發明例4 15 10 30 35 0.128 0.164 39.4 〇 本發明例5 16 10 60 45 0.124 0.163 40.1 〇 本發明例6 17 50 g/1 5.0 35〇C 10 0 12 0.160 0.205 37.2 〇 比較例11 18 10 1 15 0.145 0.200 38.1 〇 本發明例7 19 10 5 24 0.137 0.173 39.0 〇 本發明例8 20 10 10 32 0.127 0.165 38.9 〇 本發明例9 21 10 30 40 0.127 0.159 39.9 〇 本發明例10 22 10 60 50 0.125 0.160 40.8 〇 本發明例11 23 15°C 10 10 14 0.145 0.198 37.1 〇 比較例12 24 10 30 27 0.134 0.169 38.1 〇 比較例13 25 10 60 37 0.125 0.166 39.2 〇 比較例14 26 25〇C 10 10 19 0.138 0.189 38.5 〇 本發明例12 27 10 30 32 0.129 0.166 40.3 〇 本發明例13 28 10 60 43 0.127 0.162 40.0 〇 本發明例14 29 65〇C 10 10 35 0.128 0.164 40.5 〇 本發明例15 30 10 30 44 0.125 0.162 41.6 〇 本發明例16 31 10 60 51 0.123 0.160 41.8 〇 本發明例17 32 75〇C 10 10 35 0.124 0.161 40.6 X 比較例15 33 10 30 45 0.120 0.163 40.5 X 比較例16 34 10 60 52 0.121 0.158 41.0 X 比較例17 35 35〇C 30 10 20 0.143 0.185 38.5 〇 本發明例18 36 30 30 34 0.128 0.163 39.1 〇 本發明例19 37 30 60 49 0.127 0.161 40.4 〇 本發明例20 38 35°C 40 10 13 0.155 0.202 37.4 〇 本發明例21 39 40 30 28 0.132 0.167 39.0 〇 本發明例22 40 40 60 42 0.127 0.163 39.7 〇 本發明例23 41 3·5添 力口硫酸 35〇C 10 10 14 0.149 0.201 36.0 〇 比較例18 42 10 30 27 0.130 0.165 39.2 〇 比較例19 43 10 60 40 0.124 0.162 41.0 〇 比較例20 44 100 g/1 4.9 35〇C 10 10 34 0.125 0.166 40.5 〇 本發明例24 45 10 30 41 0.123 0.164 40.9 〇 本發明例25 46 10 60 50 0.121 0.163 40.8 〇 本發明例26 098113978 16 201024461[表 1-2]No. Test material use solution pH solution temperature dependence (g/mz) Time to water wash (seconds) Oxide film thickness (nm) Maximum age of formation (ran) Steel plate appearance Remarks pH buffer Zn New 1 Pie 2 1 GA — — — — — A 8 0.180 0.223 35.0 〇Comparative Example 1 2 Nanoacetic acid (20 g/L) — 2.0 added sulfuric acid 35 〇C 10 10 15 0.149 0.190 36.5 〇fcbfe Example 2 3 10 30 30 0.128 0.165 38.1 〇 Comparative Example 3 4 10 60 42 0.120 0.163 39.3 〇Comparative Example 4 5 - 5.0 Addition of sulfuric acid 35 〇C 10 10 8 0.183 0.219 35.6 〇Comparative Example 5 6 10 30 8 0.179 0.221 35.9 〇Comparative Example 6 7 10 60 8 0.180 0.217 35.9 〇Comparative Example 7 8 — 2.5 g/1 5.6 35〇C 10 10 12 0.148 0.200 36.5 〇Comparative Example 8 9 10 30 25 0.140 0.174 37.9 〇Comparative Example 9 10 10 60 32 0.132 0.163 38.9 〇Comparative Example 10 11 5 g/ 1 5.5 35〇C 10 10 18 0.138 0.187 37.6 〇 Inventive Example 1 12 10 30 32 0.123 0.166 39.1 〇 Inventive Example 2 13 10 60 43 0.122 0.163 39.5 〇 Inventive Example 3 14 10 g/1 5.2 35〇C 10 10 25 0.134 0.174 39.0 〇 Inventive Example 4 15 10 30 35 0.128 0 .164 39.4 〇 Inventive Example 5 16 10 60 45 0.124 0.163 40.1 〇 Inventive Example 6 17 50 g / 1 5.0 35 〇 C 10 0 12 0.160 0.205 37.2 〇 Comparative Example 11 18 10 1 15 0.145 0.200 38.1 〇 Inventive Example 7 19 10 5 24 0.137 0.173 39.0 〇 Inventive Example 8 20 10 10 32 0.127 0.165 38.9 〇 Inventive Example 9 21 10 30 40 0.127 0.159 39.9 〇 Inventive Example 10 22 10 60 50 0.125 0.160 40.8 〇 Inventive Example 11 23 15°C 10 10 14 0.145 0.198 37.1 〇Comparative Example 12 24 10 30 27 0.134 0.169 38.1 〇Comparative Example 13 25 10 60 37 0.125 0.166 39.2 〇Comparative Example 14 26 25〇C 10 10 19 0.138 0.189 38.5 〇Inventive Example 12 27 10 30 32 0.129 0.166 40.3 〇 Inventive Example 13 28 10 60 43 0.127 0.162 40.0 〇 Inventive Example 14 29 65〇C 10 10 35 0.128 0.164 40.5 〇 Inventive Example 15 30 10 30 44 0.125 0.162 41.6 〇Inventive Example 16 31 10 60 51 0.123 0.160 41.8 〇 Inventive Example 17 32 75〇C 10 10 35 0.124 0.161 40.6 X Comparative Example 15 33 10 30 45 0.120 0.163 40.5 X Comparative Example 16 34 10 60 52 0.121 0.158 41.0 X Comparative Example 17 35 35〇C 30 10 20 0.143 0.18 5 38.5 〇 Inventive Example 18 36 30 30 34 0.128 0.163 39.1 〇 Inventive Example 19 37 30 60 49 0.127 0.161 40.4 〇 Inventive Example 20 38 35°C 40 10 13 0.155 0.202 37.4 〇 Inventive Example 21 39 40 30 28 0.132 0.167 39.0 〇 Inventive Example 22 40 40 60 42 0.127 0.163 39.7 〇 Inventive Example 23 41 3·5 Adding strength sulfuric acid 35〇C 10 10 14 0.149 0.201 36.0 〇Comparative Example 18 42 10 30 27 0.130 0.165 39.2 〇Comparative Example 19 43 10 60 40 0.124 0.162 41.0 〇Comparative Example 20 44 100 g/1 4.9 35 〇C 10 10 34 0.125 0.166 40.5 〇Inventive Example 24 45 10 30 41 0.123 0.164 40.9 〇Inventive Example 25 46 10 60 50 0.121 0.163 40.8 〇 Inventive Example 26 098113978 16 201024461 [Table 1-2]

No. 供試 材料 使用溶液 pH 溶液 賴量 (g/m2) 水洗為止 之時間(秒) 摩麟數 最大成 形高度 (ran) 鋼板 外觀 備註 pH緩 衝劑 Zn iM. 丨 人少·^- (ran) 餅1 絲2 47 GI — — — — — — 7 0.175 0.215 35.7 〇 比較例21 48 乙義 (20 g/L) — 2.0添 加硫酸 35°C 10 10 13 0.147 0.187 36.7 〇 比較例22 49 10 30 27 0.125 0.164 38.6 〇 比較例23 50 10 60 39 0.119 0.160 39.6 〇 比較例24 51 — 2.5 g/1 5.6 35〇C 10 10 11 0.161 0.198 36.3 〇 比較例25 52 10 30 24 0.13 0.168 38 〇 比較例26 53 10 60 34 0.121 0.163 39.1 〇 _例27 54 10 g/1 5.2 35〇C 10 10 19 0.138 0.177 37.1 〇 本發明例27 55 10 30 32 0.124 0.161 38.5 〇 本發明例28 56 10 60 42 0.121 0.161 39.5 〇 本發明例29 57 50 g/1 5.0 35〇C 10 10 26 0.127 0.166 38.4 〇 本發明例30 58 10 30 36 0.122 0.163 39 〇 本發明例31 59 10 60 45 0.12 0.159 39.7 〇 本發明例32 60 EG — — — — — — 9 0.146 0.289 33.7 〇 比較例28 61 乙義 (20 g/L) — 2.0添 加硫酸 35〇C 10 10 11 0.136 0.241 34.0 〇 比較例29 62 10 30 23 0.135 0.195 36.6 〇 比較例30 63 10 60 36 0.128 0.173 37.9 〇 比較例31 64 — 2.5 g/1 5.6 35°C 10 10 12 0.140 0.199 37.0 〇 比較例32 65 10 30 23 0.131 0.181 37.2 〇 比較例33 66 10 60 31 0.131 0.159 37.5 〇 比較例34 67 10 g/1 5.2 35〇C 10 10 20 0.139 0.221 35.4 〇 本發明例33 68 10 30 35 0.132 0.195 36.9 〇 本發明例34 69 10 60 45 0.129 0.160 37.6 〇 本發明例35 70 50 g/1 5.0 35〇C 10 10 22 0.136 0.192 37.6 〇 本發明例36 71 10 30 37 0.131 0.153 39.3 〇 本發明例37 72 10 60 46 0.125 0.156 38.9 〇 本發明例38 098113978 17 201024461 根據表Μ及表l 2 (1)因 No.l 所示之試驗結果，可知悉下述事項。No. Test material using solution pH solution (g/m2) Time until water washing (seconds) Molining maximum forming height (ran) Steel sheet appearance Remarks pH buffer Zn iM. 丨人少·^- (ran) Cake 1 Wire 2 47 GI — — — — — 7 0.175 0.215 35.7 〇Comparative Example 21 48 yiyi (20 g/L) — 2.0 added sulfuric acid 35°C 10 10 13 0.147 0.187 36.7 〇Comparative Example 22 49 10 30 27 0.125 0.164 38.6 〇Comparative Example 23 50 10 60 39 0.119 0.160 39.6 〇Comparative Example 24 51 — 2.5 g/1 5.6 35〇C 10 10 11 0.161 0.198 36.3 〇Comparative Example 25 52 10 30 24 0.13 0.168 38 〇Comparative Example 26 53 10 60 34 0.121 0.163 39.3 〇_Example 27 54 10 g/1 5.2 35〇C 10 10 19 0.138 0.177 37.1 〇 Inventive Example 27 55 10 30 32 0.124 0.161 38.5 〇Inventive Example 28 56 10 60 42 0.121 0.161 39.5 〇 Inventive Example 29 57 50 g / 1 5.0 35 〇 C 10 10 26 0.127 0.166 38.4 〇 Inventive Example 30 58 10 30 36 0.122 0.163 39 〇 Inventive Example 31 59 10 60 45 0.12 0.159 39.7 〇 Inventive Example 32 60 EG — — — — — — 9 0.146 0.289 33.7 〇Comparative Example 28 61 Yiyi (20 g/L) — 2.0 added sulfuric acid 35〇C 10 10 11 0.136 0.241 34.0 〇Comparative Example 29 62 10 30 23 0.135 0.195 36.6 〇Comparative Example 30 63 10 60 36 0.128 0.173 37.9 〇Comparative Example 31 64 — 2.5 g/1 5.6 35°C 10 10 12 0.140 0.199 37.0 〇Comparative Example 32 65 10 30 23 0.131 0.181 37.2 〇Comparative Example 33 66 10 60 31 0.131 0.159 37.5 〇Comparative Example 34 67 10 g/1 5.2 35〇C 10 10 20 0.139 0.221 35.4 〇 Inventive Example 33 68 10 30 35 0.132 0.195 36.9 〇 Inventive Example 34 69 10 60 45 0.129 0.160 37.6 〇 Inventive Example 35 70 50 g / 1 5.0 35 〇 C 10 10 22 0.136 0.192 37.6 〇 Inventive Example 36 71 10 30 37 0.131 0.153 39.3 〇 Inventive Example 37 72 10 60 46 0.125 0.156 38.9 〇 Inventive Example 38 098113978 17 201024461 According to the table Μ and Table l 2 (1) The results of the test shown in No. 1 can be known as follows matter.

(2)Νο.2〜4、 Νο.48〜No.50及No.61〜No.63係使用具 有PH緩衝作用之酸性溶液的比較例。若為3G秒以上，則 摩擦係數較低’最大开》成高度亦變高，但10秒之處理，並 不滿足充分之摩擦係數下降及最大成形高度之提高。 (3)Νί)·5〜Ν〇·7係使用具有pH缓衝作用之酸性溶液之比 較例。呈現出較高之摩擦係數。 (4讲〇8〜1^〇.10、>^〇.51〜：^〇.53及1^〇.64〜：^〇.66係雖然 含有辞離子’但其含量少於本發明範圍之比較例。若為30 秒以上’則摩擦係數較低，最大形成高度亦提高，但10秒 之處理’並不滿足充分之摩擦係數下降及最大成形高度之提 高。 (5)Νο.11〜：Νο·13、Νο·54〜Νο.56&Νο.67〜Νο.6Μ|^：>^ 有辞離子之溶液進行處理的本發明例，摩擦係數下降，最大 成开〉咼度亦提高。又’ No. 14〜No. 16及No.44〜No.46係於 與No.ll〜No.13相同之處理條件下增加溶液中之鋅離子濃 度的本發明例。摩擦係數低位穩定化，最大成形高度亦進一 步增加。同樣地，No.57〜No.59及No.70〜No.72係於與 Νο·54〜No.56相同之處理條件下增加溶液中之鋅離子濃度 098113978 18 201024461 最大成形高度亦進一步 的本發月例。摩擦係數低位穩定化 增加。 fcH /7 NG22係於鋼板表面形成溶液膜，並改變實施 V麼拔Γ時間的示例。於未經保持便進行水洗的n〇.17 數僅略微下降，相對於此，於保持時間為i秒以 上之Νο.18〜Νο·22中’摩擦係數下降，伸展性亦穩定上升。 ⑺N〇.23〜Nq.4g係改變處理液溫度之例，處理液溫度較 低之N。.23〜Ng.25相比於除此以外之例，摩擦係數及最大 成形高度之提高效果不充分。另—方面，Nq32〜n〇34係 處理液溫餘高之例’雖歸擦餘或最大成形高度之增加 效果充分，但可觀察雜多處理不均，作為汽車科殼^未 呈現良好之外觀。 (8) N〇.35〜No.40係相對No.20〜No.22，改變液膜形成量 之本發明例。若以水洗為止之保持時間相同者進行比較，則 ❿於液膜量較多之情形時’雖然可獲得充分之摩擦係數下降及 最大成形高度之提高’但相比於液膜量較少之情形，摩擦係 數僅少許提高且最大成形高度亦變低。 (9) Νο·41〜No.43係使用pH低於本發明範圍之處理液的 比較例，但與No.20〜No.22相比，無法確認摩擦係數之下 降效果，亦未觀察到最大成形高度之提高。 圖5係使用表1-1及表1-2之N〇.8〜No 22及N〇 44〜 No.46，表示鋅離子濃度對氧化膜厚之影響的圖。根據圖5 098113978 19 201024461 可知’若鋅濃度為5 g/l以上，則即便保持時間較短時(例如， 10秒）’亦可充分厚地形成氧化膜厚，解決了本發明之課題， 即保持時間較短之情形時，氧化膜厚變薄。 (產業上之可利用性）(2) Νο. 2 to 4, Νο. 48 to No. 50, and No. 61 to No. 63 are comparative examples using an acidic solution having a pH buffering action. If it is 3 Gsec or more, the lower friction coefficient 'maximum opening' becomes higher, but the treatment of 10 seconds does not satisfy the sufficient reduction of the friction coefficient and the increase of the maximum forming height. (3) Νί)·5~Ν〇·7 is a comparative example using an acidic solution having a pH buffering effect. A higher coefficient of friction is exhibited. (4 lectures 〜8~1^〇.10,>^〇.51~:^〇.53 and 1^〇.64~:^〇.66 although containing the word ion' but its content is less than the scope of the present invention In the comparative example, if it is more than 30 seconds, the friction coefficient is lower and the maximum forming height is also increased, but the processing of 10 seconds does not satisfy the sufficient reduction of the friction coefficient and the increase of the maximum forming height. (5) Νο.11~ : Νο·13, Νο·54~Νο.56&Νο.67~Νο.6Μ|^:>^ In the example of the invention in which the solution of the ionic ion is treated, the friction coefficient is decreased, and the maximum opening degree is increased. Further, 'No. 14 to No. 16 and No. 44 to No. 46 are examples of the present invention in which the zinc ion concentration in the solution is increased under the same treatment conditions as No. 11 to No. 13. The friction coefficient is stabilized at a low level. The maximum forming height is further increased. Similarly, No. 57 to No. 59 and No. 70 to No. 72 increase the zinc ion concentration in the solution under the same treatment conditions as Νο·54 to No. 56 098113978 18 201024461 The maximum forming height is further increased by the monthly example. The friction coefficient is stabilized at a low level. fcH /7 NG22 forms a solution film on the surface of the steel sheet and changes An example of the implementation of the V-drawing time. The number of n〇.17 which was washed without being maintained was only slightly decreased. In contrast, the friction coefficient decreased in the Νο.18~Νο·22 with a holding time of i seconds or more. (7) N〇.23~Nq.4g is an example of changing the temperature of the treatment liquid, and the temperature of the treatment liquid is lower than N..23~Ng.25, compared with other examples, the friction coefficient and the maximum The effect of improving the forming height is not sufficient. On the other hand, the example of the Nq32~n〇34 system treatment liquid temperature is high, although the effect of increasing the rubbing residue or the maximum forming height is sufficient, but the heterogeneous processing unevenness can be observed as a car. (8) N〇.35~No.40 is a case of the present invention in which the amount of liquid film formation is changed with respect to No. 20 to No. 22. If the holding time is the same with water washing, the same is true. In comparison, when the amount of the liquid film is large, 'although a sufficient friction coefficient and an increase in the maximum forming height are obtained', the friction coefficient is only slightly increased and the maximum forming height is compared with the case where the amount of the liquid film is small. It also becomes lower. (9) Νο·41~No.43 uses pH lower than the present invention In the comparative example of the treatment liquid in the range, compared with No. 20 to No. 22, the effect of lowering the friction coefficient could not be confirmed, and the increase in the maximum forming height was not observed. Fig. 5 shows the use of Table 1-1 and Table 1 2N〇.8~No 22 and N〇44~ No.46, which show the effect of zinc ion concentration on the oxide film thickness. According to Fig. 5 098113978 19 201024461, if the zinc concentration is 5 g/l or more, Even when the holding time is short (for example, 10 seconds), the thickness of the oxide film can be sufficiently thick, and the problem of the present invention is solved, that is, when the holding time is short, the thickness of the oxide film is reduced. (industrial availability)

根據本發明，即便於短時間之製造條件下，亦可穩定製造 省工間、衝壓成形時之滑動阻抗小且具有優異之衝壓成形性 的鍍鋅鋼板。*且’例如即便製造成形荷$較高易於產生模 具擦傷之高強歧_板時，衝壓成科之祕阻抗亦較 小，亦可具有優異之衝壓成形性。因衝壓成形性優異，故而 可以汽車車體用途為中心適用於廣泛領域。 【圖式簡單說明】 圖1係表使狀氧化物層形成處理設備之主 要部分的圖。 圖2係表示摩擦係數測定裝置之概略前視圖。According to the present invention, it is possible to stably manufacture a galvanized steel sheet which is labor-saving, has a small sliding resistance at the time of press forming, and has excellent press formability even under a short period of manufacturing conditions. * And, for example, even when a high-strength plate having a high molding load is likely to cause a mold scratch, the film has a small impedance and can have excellent press formability. Because of its excellent press formability, it can be applied to a wide range of applications centering on automotive body applications. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a main portion of a process for forming an oxide layer. Fig. 2 is a schematic front view showing a friction coefficient measuring device.

圖3係表示® 2巾之調整桿做.尺寸之概略立體圖 圖4係表示圖2中之調整桿形狀.尺寸之概略立體圖 圖5係表不辞離子濃度對氧化膜厚之影響的圖。 【主要元件符號說明】 清洗槽 2 3 4 溶液槽 擠壓觀 淋式水洗裝置 098113978 20 201024461 8 11 12 13 14 15 16 # 17Fig. 3 is a schematic perspective view showing the size of the adjusting rod of the 2 towel. Fig. 4 is a schematic perspective view showing the shape of the adjusting rod in Fig. 2. Fig. 5 is a view showing the influence of the ion concentration on the thickness of the oxide film. [Main component symbol description] Cleaning tank 2 3 4 Solution tank Extrusion view Shower water washing device 098113978 20 201024461 8 11 12 13 14 15 16 # 17

18 19 S 乾燥機 樣本 樣本台 滑台 滚筒 滑台支撐台 調整桿 第1荷重元 第2荷重元 執道 鋼板 098113978 2118 19 S Dryer Sample Sample Table Slide Table Roller Table Support Table Adjustment Rod 1st Load Cell 2nd Load Element Execution Plate 098113978 21

Claims (1)

201024461 七、申請專利範圍： 1 ·種鑛鋅鋼板之製造方法，其係對鋼板實施鍍鋅之後， 於水溶液中進行接觸處理，並於接觸處理結束之後保持 6〇秒’然後進行水洗.乾燥’藉此於鋼板表面减氧化物層 者，其特徵在於：對鍍鋅鋼板進行接觸處理之上述水溶液， 以鋅離子濃度為5〜100 g/Ι之範圍含有鋅離子，且pH^4 〜6,液體溫度為2〇〜7(rc。 ’''4 2. 如申晴專利範圍第1項之鍍鋅鋼板之製造方法，其中 上述水溶液中含有鋅之硫酸鹽。 懸 3. 如申請專利範圍第1或2項之鍍鋅鋼板之製造方法，其 中，與上述水溶液接觸後形成於鋼板表面之液膜為$〜 g/m2。 一、〜3〇 範園苐 且於鋼 金屬成〇 種鍍鋅鋼板，其特徵在於：其係藉由申請專 1至3項4m工 _ J K T饪〜項之鍍鋅鋼板之製造方法而製造者， 表面开/成平均厚度10 nm以上之主要含有辞作為 分之氧化物層。 098113978 22201024461 VII. Scope of application: 1 · The method for manufacturing a kind of zinc ore plate, which is subjected to galvanization after the galvanization of the steel plate, and is contacted in an aqueous solution, and kept for 6 sec seconds after the end of the contact treatment, and then washed with water. The oxide layer on the surface of the steel sheet is characterized in that the aqueous solution which is subjected to the contact treatment on the galvanized steel sheet contains zinc ions in a range of a zinc ion concentration of 5 to 100 g/Ι, and has a pH of 4 to 6, The temperature of the liquid is 2〇~7 (rc. '''4 2. The method for producing a galvanized steel sheet according to the first paragraph of the Shenqing patent scope, wherein the above aqueous solution contains zinc sulfate. Hanging 3. As claimed in the patent scope The method for producing a galvanized steel sheet according to the first or second aspect, wherein the liquid film formed on the surface of the steel sheet after contact with the aqueous solution is $~g/m2. 1. 〜3〇范园苐 and galvanized in steel metal A steel sheet characterized in that it is manufactured by applying a method of manufacturing a galvanized steel sheet of 1 to 3 pieces of 4m _JKT cooking to the surface, and the surface opening/forming average thickness of 10 nm or more is mainly included. Oxide layer. 098 113978 22
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